DE3000076A1 - GROWTH-PROMOTING AND PLANT-PROTECTING AGENTS - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT - ^ f * ■ Dr.TG/ge HOE 8o / f Growth promoting and plant protecting agents oUUUU / b

The present application relates to growth promoting co tel, which are characterized by a content of compounds of the formula I:

Ar-X- C _n H _2n - R (I),

wherein Ar is phenyl, optionally mono- to trisubstituted by chlorine or bromine and / or monosubstituted by CF ₃₇ (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) alkoxy, CN, NO ₂ , phenyl, benzyl or phenoxy in the para position, where benzyl or phenoxy for their part can be substituted up to twice in the phenyl nucleus by chlorine, bromine, CN, NO “or CF_; or naphthyl, optionally substituted once or twice by chlorine, bromine, (C ₁ -C ₄ ) alkyl, CN, NO ₃ or CF ₃ ;

X: oxygen, sulfur, SO or SO "; n: 1, 2 or 3;
R: CN or

R ₁ : H, (C ₁ -C ₄ ) alkyl which is optionally substituted by chlorine, bromine, CN, NO ₂ , -COO (C ₁ -C ₄ ) alkyl or -CONR ₂ R-; -COR., -CONR ₀ R ,, -SO ₀ R ₁ . or -P (ORj ₀ ;

0 (S)

Rp and R- .: H or (C ₁ -C ₁₈ ) alkyl or together with the nitrogen atom a piperidino, pyrrolidino or morpholino radical;

R ₄ : (C ₁ -C ₃ ) alkyl, phenyl or benzyl, where the latter can be monosubstituted or disubstituted in the phenyl radical by chlorine, bromine, CN, NO ₂ , CF ₃ or (C _{-C 0} ) alkyl;

T30036 / 0a30

R ₅ ; (C ₁ -C ₄ ) alkyl, phenyl or tolyl, as well as JUUUU / 0 Rg! (C ₁ -C ₄ ) alkyl.

The compounds of the general formula I with R = C (NH -) - -NOH can also be used in the form of their metal salts or acid addition products.

Preferred herbicidal antidotes are those compounds of general formula I in which

Ars halophenyl, (subst) phenoxyphenyl or naphthyl; X: oxygen and

CH ₀ -CH "-or-CHCH ,, mean,
η 2n 2 ο

Preferred individual compounds of the general formula I may be mentioned, for example;

4-chlorophenoxyacetonitrile and acetamidoxime, ck- (4-chlorophenoxy) propionitrile and propionamidoxime, 2, 4-dichlorophenoxyacetonitrile and acetamidoxime, 3,4-dichlorophenoxyacetonitrile and acetamidoxime, 4-bromo-2-chlorophenoxyacetonitrile and acetamidoxime, Trichlorphenoxyacetamidoxim, 0 ^ - (4-bromo-2-chloro) and propionamidoxime phenoxypropionitril, 4-chloro-2-methylphenoxyacetonitril and acetamide oxime, 2-chloro-4-methylphenoxyacetonitril and-acetamidoxime, 2, 3 and Dichlorphenoxyacetonitril-acetamidoxime ,

2-naphthyloxy-acetonitrile and acetamidoxime, C ^ - (2j4-dichlorophenoxy) propionitrile and propionamidoxime, 4-chlorophenylthioacetonitrile and acetamidoxime, 3j 4-dichloro-phenylthio-acetonitrile and -acetamidoxime, 3/4-dichlorophenylsulfinyl acetonitrile and acetamidoxime, 3j 4-dichlorophenylsulfonylacetonitrile and acetamidoxime,

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O-acetyl-4-chlorophenoxy-acetamidoxime, 3 U U U U / D

O- (N-methyl-carbaraoyl) -2,4-dichlorophenoxyacetamidoxime, 0- (tf- octadecyte-carbamoyiO ^^ - dichlorophenoxyacetamidoxime, 0- (N ₇ N-dimethyl-carbamoyl) -2, 4-dichlorophenoxyacetamidoxime, op-toluenesulfonyl -2,4-dichlorophenoxyacetamidoxime,

The compounds of general formula I are as such largely known and can be produced by processes that are likewise known or by analogy with these processes / J. At the. Chem. Soc. J59_, 1690 (1947); Rocz. Chem. 45, 345 (1971); U.S. Patent No. 3,139,455; U.S. Patent 3,547,621; U.S. Patent 3,644,523; FR-PS 1,572,961; JA-PS 42-9944; JA-PS 72 37 540_7. Some of them have already been proposed for herbicidal purposes.

Surprisingly, it has been found that the compounds of the formula I in low doses have growth-promoting and plant-protecting properties. They have the property of stimulating the growth of germinating seeds and young plants, which is expressed in an enlargement of the root system, increased photosynthesis and faster development of the above-ground parts of the plant. Use at a later stage of plant development results in increased fruit set , faster maturity and improved crop yield. If the seeds or seedlings of the desired plant are treated with compounds of the formula I, their ability to compete with the unstimulated weed flora is strengthened. Finally, the treatment improves the growth chances of crops under unfavorable conditions, ζ. B. on nutrient-poor soils.

Another important possible use of the compounds of the formula I lies in their * phytotoxic property Side effects of pesticides, especially herbicides, to reduce or eliminate when used selectively in crops of useful plants. This can

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area of application of conventional pesticides quite considerably be enlarged. Compounds that have the property of protecting against phytotoxic damage by crops Protecting pesticides without impairing the pesticidal effect of these agents becomes antidotes or safeners called.

Herbicidal antidotes are so far only a few examples such as N, N-diallyl-2,2-dichloroacetamide / Can. J. Pl. Sci. 5-2, 707 (1972); DE-PS 22 18 0927 or naphthalic anhydride / weed. May be. J_9, 565 (1971); US Pat. No. 3,131,5097 and some oxime ethers and esters / DE-OS 28 08 3127, in particular in connection with thiocarbamate herbicides, are known / s. on this also FM Pallos and JE Cassida, "Chemistry and Action of Herbicide Antidots" / Academic Press, New York / London, 197 ^ 7

Herbicides / their phytotoxic side effects using compounds of formula I can be reduced, are, for. B.

Phenylureas, triazines, carbamates, thiocarbamates, haloacetanilides, substituted phenoxy and phenoxyphenoxycarboxylic acid esters as well as pyridyloxy, benzoxazyloxy or Benzthiazolyloxy-phenoxycarboxylic acid esters, also benzoic acid derivatives, dimedonoxime derivatives and dinitroaniline derivatives =

For example, herbicides from the following classes may be mentioned, without this being intended to impose a restriction:

A) Herbicides of the phenoxycarboxylic acid ester type such as

{£ - / 4 ~ - (2,4-dichlorophenoxy) -phenoxy_7-propionic acid methyl ester,

o <- / 4- (4-Bromo-2-chlorophenoxy) -phenoxy_7-propionic acid methyl ester /

o (- / 4 "-Trifluoromethylphenoxy) -phenoxy_7-propionic acid methyl ester ₇

C ^ - / 4 "- (2-chloro-4-trifluoromethylphenoxy) -phenoxy_7-propion-

acid methyl ester, - 5 -

13003670030

οζ - £ ξ- (2,4-dichlorobenzyl) -phenoxy_7-propionic acid methyl ester,

^ f - / 4- (4-trifluoromethylphenoxy) -phenoxy _ / - 2-pentene-1 carboxylic acid ethyl ester,

oi - / ¥ - (3,5-Dichlorpyridy1-2-oxy) -phenoxy ^ -propionic acid ethyl ester,

d - / 4- (6-chlorobenzoxazol-2-yl-oxy) -phenoxy_7-propionic acid ethyl ester or

d -JJi- (6-chlorobenzothiazol-2-yl-oxy) -phenoxyZ-propionic acid methyl ester

B) chloroacetanilide herbicides such as

N-methoxymethyl 1-2, e-diethyl-chloroacetanilide or N- / 3 " ¹ -methoxyprop- (2 ') -yl / ^ - methyl-G-ethyl-chloroacetanilide

C) thiol carbamates such as

S-Ethy1-N, N-dipropy1thiocarbamate or S-ethyl-N / N-diisobutyl thiocarbamate

D) Diredone derivatives such as

2- (N-ethoxybutyrimidoyl) -5- (2-ethylthiopropyl) -3-hydroxy-2-cyclohexen-1-one or

2- (1-Allyloxyiminobutyl) -4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol

E) Dinitroaniline-type herbicides such as

NjN-di-n-propyl-2 _y 6-dinitro-4-trifluoromethyl aniline

130036 / Θ030

For use, the compounds of the formula I can be mixed with customary formulation auxiliaries to form dusts, wettable powders, Dispersions, emulsion concentrates, etc. are prepared that contain the active ingredient in concentrations of 2 - 80% and are either used as such (dusts, pellets) or in a solvent before use (Water) can be dissolved or dispersed.

The quantity ratio of antidote: active ingredient can be between 0.01 and 10 parts of antidote within wide limits Part of herbicide sway. The optimal amounts of herbicide and antidote in each case depend on the type of herb used Herbicide or antidote and the type of crop to be treated and can be passed through from case to case determine appropriate tests.

The main areas of use for the compositions according to the invention are above all crops of cereals (wheat, rye, barley, oats), rice , maize, sorghum, but also cotton, sugar beet, sugar cane, soybean and others.

The agents according to the invention can, depending on their properties for pretreatment of the seeds of the cultivated plant (dressing of the seeds or the cuttings) or before Seeds can be used in the seed furrows or as a tank mix before or after the plants emerge. Ahead running treatment includes both the treatment of the acreage before sowing and the treatment of the sown, but not yet overgrown acreage. Basically, the antidote can be before, after, or at the same time be applied with a herbicide, but the simultaneous application in the form of tank mixes or is preferred if necessary finished formulations.

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example 1

Under field conditions, barley and egg oats in pots were grown up to the 4-leaf stage and then treated with a test herbicide and an antidote according to the invention. The active ingredients were in each case applied to the test plant in the form of aqueous emulsions or suspensions which had been prepared from formulated emulsion _{concentrates or wettable powders 7 either individually or together.} After treatment, the plants were under good growth conditions (18 - C, normal irrigation 23 ⁰⁾ is held and 3 weeks later, the Wachstumsbeeinflußung was scored by the plant damage was estimated as a percentage. The results (see Table 1) make it clear that the barley is protected from damage by the herbicide by the antidote without the effectiveness of the herbicide against wild oats being impaired.

Table 1

Effectiveness of the connections (harmful effect in%)

Compound dose kg AS / ha barley wild oats

H ₁ 1 0 93

2 12 100

4 28 100

Αχ (K 5 0 0

H ₁ + A ₁ 1 + 0.5 2 + 0.5 4 + 0.5

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0 95 0 100 0 100

link

Dose kg AS / ha

^ 2

H ₁ + A ₂

A ₃

H ₁ + A ₃

0.5

1 + 0.5

2 + 0.5 4 + 0.5

0.5

1 + 0.5 2 + 0.5 4 + 0.5

0.5 barley

Wild oats

0 93 0 100 0 100

0 90 0 100 0 1 & 0

1 + 0 .5 2 0 93 2 + 0 .5 0 100 4th + 0 .5 .0 10C

H = herbicide

A = antidote

Diclofop-methyl

(see DE-OS 22 23 894)

0 038/0030

Example 2

Cultivated and weed plants were sown in pots and grown in the greenhouse to the 3-leaf stage. The herbicidal antidotes were used as an aqueous ·. Suspensions applied in the indicated doses to the green parts of the test plants. Immidiatly after (after the spray mixture had dried on) the spraying was carried out with the corresponding test herbicide.

After a period of about 3 weeks in the greenhouse, the damage to the crop plants and weeds was observed rated visually in comparison to the untreated controls. As can be seen from Table 2, corn is against the damage caused by herbicidal compounds (agricultural chemicals) effectively protected by the use of antidotes.

Table 2

Compound dose kg AS / ha% damage

Echinocloa Zea mays crus-galli

0.25 0.20 0.15

100
100
100

30th

^{+ A} 5 O .25 + 1. 100 O .20 + 1, 100 O .15 + 1. 100 H = herbicide A ⁼ .0 .0 .0 Antidote

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- 10 -

^H 2 ^{= Br}

0-CH-COOCH-. ι -J

CH ₃

(see DE-OS 26 01 548)

= Cl

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- 11 -

Claims (7)

HOE 80 / f 001 claims 3000076 1) Growth promoting and phytoprotective agents, labeled by a Gehali: to compounds of the formula I. Ar-X- C _n H _2n - R (I), wherein Ar is phenyl / optionally mono- to trisubstituted by chlorine or bromine and / or _{monosubstituted by CF 37} (C ₁ -C ₄ J-AlkYl, (C ₁ -C ₄ ) alkoxy, CN, NO «, phenyl, benzyl or Phenoxy in the para position, where benzyl or phenoxy in turn can be substituted up to twice in the phenyl nucleus by chlorine, bromine, CN, NO «or CF-; or naphthyl, optionally substituted once or twice by chlorine, bromine, (C ₁ - C ₄ ) alkyl, CN, NO ₂ or CF ₃ ; X: oxygen, sulfur, SO or SO ₃ ; n: 1/2 or 3;
R: CN or R-: H, (C ₁ -C ₄ ) alkyl, which is optionally substituted by chlorine, bromine, CN, NO ₃₇ -COO (C ₁ -C ₄ ) alkyl or -CONR ₃ R _3; -COR ₄ , -CONR ₃ R ₃ , -SO R ₅ or -P (ORg) ₃ ; 0 (S) R ₀ and R ^: H or (C ₁ -C ₁₀ ) alkyl or together with the nitrogen atom a piperidino; Pyrrolidino or morpholino; R ₄ : (CC ₃ ) alkyl, phenyl or benzyl, it being possible for the latter to be monosubstituted or disubstituted in the phenyl radical by chlorine, bromine, CN, NO ₃ , CF ₃ or (C ₁ -C ₃ ) alkyl; -12 - 130036/0030 BAD ORJQiMAL R ₅ : (C ₁ -C ₄ ) alkyl, phenyl or tolyl, and R ₆ : (C ₁ -C ₄ ) alkyl. 2) means according to claim 1, characterized by a content of compounds of the formula I in which Ar: halophenyl., Phenoxyphenyl (where the Phenoxy radical by Cl., Br, CN, NO ₀ , or CF-. can be substituted up to twice) or naphthyl X: oxygen
C _n H ₂ : -CH ₂ - or -CH (CH ₃ ) and the remaining radicals have the meaning given. 3) Method of promoting plant growth, thereby characterized in that the plants, plant parts or plant nutrient media with a compound according to the claims 1 and 2 dealt with. 4) Method of protecting crops against phytotoxic Side effects of plant protection agents, characterized in that the plants, plant parts or plant nutrient media with a compound according to claim 1 or 2 before, after or simultaneously with Pesticides treated. 5) Method according to claim 4 _y , characterized in that the crop protection product is a herbicide. 6) Method according to claim 5 _7, characterized in that the herbicide an active ingredient from the series of phenoxycarboxylic acid esters is. 7) Method according to claim 5, characterized in that the herbicide - 13 - 130036/0030 c £ - / 4- (2,4-dichlorophenoxy) ~ phenoxy _ / - propionic acid methyl ester, ^ -JA- (4-Bromo-2-chlorophenoxy) -phenoxy_7- propionic acid methyl ester, et - / 4- (4-Trifluormethy! Phenoxy) -phenoxy_7-propionic acid methyl ester, C ^ - / 4 ~ - (2-chloro-4 -trif luoromethylphenoxy) -phenoxy _ / - propionic acid methyl ester, c / - / 4- (2,4-dichlorobenzyl) -phenoxy _ / - propionic acid methyl ester, "$ * - £% - (4-trifluoromethylphenoxy) -phenoxy _ / - 2-pentene-1-carboxylic acid ethyl ester / C ^ -fT- (3/5-dichloropyridyl-2-oxy) -phenoxy_7-propionic acid ethyl ester / d - / Ϊ- (6-chlorobenzoxazol-2-yl-oxy) -phenoxy_7-propionic acid ethyl ester or C ^ - / 4- (benzthiazol-2-yl-oxy) -phenoxyj ^ -propionic acid methyl ester 130036/0030